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Theoretical and experimental insights into cycloaddition reactions

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Organic Chemistry

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 79))

Abstract

In this article, a description has been given of theoretical and experimental investigations of the factors beyond frontier molecular orbital interactions which are important in influencing mechanisms, rates, and regioselectivities of cycloadditions and related reactions of unsaturated systems. Closed-shell repulsion, geometrical distortions, polarization, and secondary orbital interactions have all been shown to be influential. Electrostatic interactions and correlation effects have not been discussed, but will provide further refinements — or confusion, depending upon the reader's point of view! As Professor Huisgen recently commented, there are now a distressingly large number of “buttons to push”, to explain various phenomena91). This is, indeed, the case at the present time, primarily due to our limited knowledge about the magnitudes of these many effects. The cases discussed here constitute examples where the cited effects seem to prevail over others, but similar effects will be present to some extent in all reactions. Our current research efforts constitute attempts to understand more generally when these effects are significant, and to be able to understand and predict rates and products of organic reactions.

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References and Notes

  1. Dewar, M. J. S., Griffin, A. C., Kirschner, S.: J. Am. Chem. Soc. 96, 6225 (1974)

    CAS  Google Scholar 

  2. Note added in proof: MINDO/3 calculations now suggest that there is a true biradical intermediate in the Diels-Alder reaction: Dewar, M. J. S., Olivella, S., Rzepa, H. S.: J. Am. Chem. Soc. 100, 5650 (1978)

    CAS  Google Scholar 

  3. Townshend, R. E., Ramunni, G., Segal, G., Hehre, W. J., Salem, L.: J. Am. Chem. Soc. 98, 2190 (1976)

    Article  CAS  Google Scholar 

  4. Dewar, M. J. S.: Disc. Farad. Soc. 62, 197 (1977)

    CAS  Google Scholar 

  5. Poppinger, D.: J. Am. Chem. Soc. 98, 7468 (1975); Aust. J. Chem. 29, 465 (1976)

    Google Scholar 

  6. Caramella, P., Houk, K. N., Domelsmith, L. N.: J. Am. Chem. Soc. 99, 4511 (1977)

    CAS  Google Scholar 

  7. Basilevsky, M. V., Shamov, A. G., Tikhomirov, V. A.: J. Am. Chem. Soc. 99, 1369 (1977); Gordon, M. D., Fukunaga, T., Simmons, H. E.: J. Am. Chem. Soc. 98, 8401 (1976)

    Google Scholar 

  8. Mulliken, R. S.: J. Am. Chem. Soc. 72, 4493 (1950); Müller, K., Helv. Chim. Acta 53, 1112 (1970)

    CAS  Google Scholar 

  9. Epiotis, N. D., Yates, R. L.: J. Am. Chem. Soc. 98, 461 (1976)

    CAS  Google Scholar 

  10. McIver, J. W., Jr.: J. Am. Chem. Soc., 94, 4782 (1972); Acct. Chem. Res. 7, 73 (1974)

    CAS  Google Scholar 

  11. Houk, K. N., in: Marchand, A. P., Lehr, R. E.: Pericyclic reactions. New York: Academic Press: 1977, Vol. II, pp. 181–271

    Google Scholar 

  12. Firestone, R. E.: Tetrahedron 39, 3009 (1977)

    Google Scholar 

  13. Bartlett, P. D.: Science 159, 833 (1968); Bartlett, P. D., Jacobson, B. M., Walker, L. E.: J. Am. Chem. Soc. 95, 146 (1973) and references therein

    CAS  Google Scholar 

  14. Mark, V.: J. Org. Chem. 39, 3179 (1974)

    CAS  Google Scholar 

  15. Jorgensen, W. L.: unpublished results cited in Ref.15) of Ref.2)

    Google Scholar 

  16. Fukui, K.: Topics Curr. Chem. 15, 1 (1970), pp. 26–28

    Google Scholar 

  17. Evans, M. G., Polanyi, M.: Trans. Farad. Soc. 34, 11 (1938)

    CAS  Google Scholar 

  18. Takatsuki, K., Murata, I., Kitahara, Y.: Bull. Chem. Soc. Japan 43, 966 (1970)

    CAS  Google Scholar 

  19. Houk, K. N.: unpublished results

    Google Scholar 

  20. Seidl, H., Huisgen, R., Knorr, R.: Chem. Ber. 102, 904 (1969); Huisgen, R., Seidl, H., Wulff, J.: Chem. Ber. 102, 915 (1969)

    CAS  Google Scholar 

  21. Houk, K. N., Sims, J., Duke, R. E., Jr., Strozier, R. W., George, J. K.: J. Am. Chem. Soc. 95, 7287 (1973); Houk, K. N., Sims, J., Watts, C. R., Luskus, L. J.: J. Am. Chem. Soc. 95, 7301 (1973)

    CAS  Google Scholar 

  22. Sustmann, R.: Tetrahedron Letters 1971, 2717

    Google Scholar 

  23. Sims, J., Houk, K. N.: J. Am. Chem. Soc. 95, 5798 (1973); Houk, K. N.: Accounts Chem. Research 8, 361 (1975)

    CAS  Google Scholar 

  24. Houk, K. N., Bimanand, A., Mukherjee, D., Sims, J., Chang, Y.-M., Kaufman, D. C., Domelsmith, L. N.: Heterocycles 7, 293 (1977)

    CAS  Google Scholar 

  25. Houk, K. N., Caramella, P., Munchausen, L. L., Chang, Y.-M., Battaglia, A., Sims, J., Kaufman, D. C.: J. Electron Spectrosc. and Related Phenomen. 10, 441 (1977)

    CAS  Google Scholar 

  26. Barkovich, A. J., Vollhardt, K. P. C.: J. Am. Chem. Soc. 98, 2667 (1976); Vollhardt, K. P. C.: Accounts Chem. Res. 10, 1 (1977); Barkovich, A. J., Strauss, E. S., Vollhardt, K. P. C.: J. Am. Chem. Soc. 99, 8321 (1977)

    Article  CAS  Google Scholar 

  27. Fields, E. K., Meyerson, S.: Tetrahedron Lett. 1967, 571 and references therein

    Google Scholar 

  28. Gandour, R. W., Strozier, R. W., Houk, K. N.: submitted for publication

    Google Scholar 

  29. Wright, J. S.: Chem. Phys. Letters 6, 476 (1970); Can. J. Chem. 53, 549 (1975)

    CAS  Google Scholar 

  30. Dixon, D. A., Stevens, R. M., Herschbach, D. R.: Disc. Farad. Soc. 62, 110 (1977)

    CAS  Google Scholar 

  31. Caramella, P., Houk, K. N.: J. Am. Chem. Soc. 98, 6397 (1976)

    Article  CAS  Google Scholar 

  32. Caramella, P., Gandour, R. W., Hall, J. A., Deville, C. G., Houk, K. N.: J. Am. Chem. Soc. 99, 385 (1977)

    CAS  Google Scholar 

  33. Gandour, R. W., Caramella, P., Santiago, C., Houk, K. N.: submitted for publication

    Google Scholar 

  34. Dewar, M. J. S., Turchi, I. J.: J. Chem. Soc. Perkin II, 724 (1977)

    Google Scholar 

  35. Padwa, A.: Accounts Chem. Research 9, 371 (1976) and references therein

    CAS  Google Scholar 

  36. Burger, K., Thenn, W., Müller, E.: Angew. Chemie, Int. Ed. Engl. 12, 155 (1973); Burger, K., Einhellig, K.: Chem. Ber. 106, 3421 (1973); Burger, K., Einhellig, K., Süss, G., Gieren, A.: Angew. Chem., Int. Ed. Engl. 12, 156 (1973)

    Google Scholar 

  37. Padwa, A., Nahm, S., Sato, E.: J. Org. Chem. 43, 1664 (1978) and references therein

    CAS  Google Scholar 

  38. Padwa, A., Ku, A., Mazzu, A., Wetmore, S. I., Jr.: J. Am. Chem. Soc. 98, 1948 (1976)

    Google Scholar 

  39. Padwa, A., Carlsen, P. H. J., Su, S.: J. Am. Chem. Soc. 99, 2798 (1977)

    CAS  Google Scholar 

  40. Turner, D. W., Baker, C., Baker, A. D., Brundle, C. R.: Molecular photoelectron spectroscopy. New York: Wiley Interscience 1970

    Google Scholar 

  41. Jordan, K. D., Burrow, P. D.: Accounts Chem. Research II, 341 (1979)

    Google Scholar 

  42. Strozier, R. W., Caramella, P., Houk, K. N.: J. Am. Chem. Soc., in press

    Google Scholar 

  43. Weber, J., McLean, A. D.: J. Am. Chem. Soc. 98, 875 (1976) report the acetylene hydrogens are bent 0.9∘ out of linearity in bridged protonated acetylene, while an angle of 2.5∘ is predicted in Hopkinson, A. C., Yates, K., Csizmadia, I. G.: J. Chem. Phys. 1971, 3835

    Article  CAS  Google Scholar 

  44. Lathan, W. A., Curtiss, L. A., Hehre, W. J., Lisle, J. B., Pople, J. A.: Prog. Phys. Org. Chem. 11, 175 (1974) report each hydrogen is bent 1.3∘ out of planarity in bridged protonated ethylene

    CAS  Google Scholar 

  45. Walsh, A. D.: J. Chem. Soc. 1953, 2288; see also Gimarc, B. M.: Accts. Chem. Research 7, 384 (1974)

    Google Scholar 

  46. Hoffmann, R.: Tetrahedron 22, 521 (1966); Kammer, W. E.: Chem. Phys. Lett. 6, 529 (1970); Tatsumi, K., Fueno, T., Nakamura, A., Otsuka, S.: Bull. Chem. Soc., Japan 49, 2170 (1976); Gavezzotti, A., Simonetta, M.: Chem. Phys. Lett. 48, 434 (1977)

    CAS  Google Scholar 

  47. Ingold, C. K., King, G. W.: J. Chem. Soc. 1953, 2702, 2725; Innes, K. K.: J. Chem. Phys. 22, 863 (1954); Hardwick, J. L., Ramsay, D. A.: Chem. Phys. Lett. 48, 399 (1977)

    Google Scholar 

  48. Duchesne, J.: J. Chem. Phys. 18, 1120 (1950)

    Article  CAS  Google Scholar 

  49. Burnelle, L.: Tetrahedron 20, 2403 (1964); 21, 49 (1965)

    Article  CAS  Google Scholar 

  50. Baldwin, J. E.: J. Chem. Soc., Chem. Comm. 1976, 734

    Google Scholar 

  51. Dale, J., in: Viehe, H. G.: Acetylenes. New York: Marcel Dekker, Inc. 1969, Chap. 1

    Google Scholar 

  52. Earlier explanations of the trans-stereoselectivity of nucleophilic additions to ethylenes cited frontier MO symmetry (Fukui, K.: Tetrahedron Letters 1965, 2427), steric effects, or electrostatic factors (Benson, S. W., Haugen, G. R.: J. Am. Chem. Soc. 87, 4026 (1965). A lucid discussion of these is given in Ref.52), pp. 148–157

    Google Scholar 

  53. Dykstra, C. E., Arduengo, A. J., Fukunaga, T.: J. Am. Chem. Soc., in press

    Google Scholar 

  54. Note added in proof: with 3×3 CI, our calculations also predict a 16 kcal/mol activation barrier41)

    Google Scholar 

  55. Miller, S. I., Tanaka, R., in: Thyagarajan, B. S. (ed.): Selective organic transformations. New York: Wiley-Interscience 1970, Vol. I, p. 141

    Google Scholar 

  56. For example, 1,5-hexadiene (W. von E. Doering, Toscano, V. G., Beasley, G. H.: Tetrahedron 27, 5299 (1971)), and 1,5-hexadiyne (Huntsman, W. D., Wristers, J. J.: J. Am. Chem. Soc. 89, 342 (1967)), both undergo Cope rearrangements with an activation energy of 34 kcal/mol, and the relative rates of oxy-Cope rearrangements of hexa-1,5-dien-3-ol, hex-1-en-5-yn-3-ol, and hexa-1,5-diyn-3-ol are 1:2.6: 5.4 (Viola, A., McMillan, J. H., Proverb, R. J., Yates, B. L.: Chem. Comm. 1971, 936

    CAS  Google Scholar 

  57. Houk, K. N.: J. Am. Chem. Soc. 95, 4092 (1973); Houk, K. N., Strozier, R. W.: J. Am. Chem. Soc. 95, 4094 (1973)

    CAS  Google Scholar 

  58. Imamura, A., Hirano, T.: J. Am. Chem. Soc. 97, 4192 (1975); Libit, L., Hoffmann, R.: J. Am. Chem. Soc 96, 1370 (1974)

    Article  CAS  Google Scholar 

  59. The relative sizes of the HOMO coefficients of electron-deficient alkenes are different in various types of calculations: see Ref.10) and references therein

    Google Scholar 

  60. Houk, K. N., Domelsmith, L. N., Strozier, R. W., Patterson, R. T.: J. Am. Chem. Soc. 100, 6531 (1978)

    Article  CAS  Google Scholar 

  61. Bohlmann, F., Mathar, W., Schwarz, H.: Chem. Ber. 110, 2928 (1977); see also Bohlmann, F., Förster, J., Fischer, C. H.: Annalen 1976, 1487

    Google Scholar 

  62. Examples of this type include the reactions of 2,6-dimethyl-p-benzoquinone with piperylene (Schmidt, C., Sabnis, S.: unpublished results referred to in: Liu, T. T. H., Schmidt, C.: Tetrahedron 27, 5289 (1977)) and 6-methoxy-1-vinyl-2,3-dihydronaphthalene (Dickinson, R. A., Kubela, R., McAlpine, G. A., Stojanac, Z., Valenta, Z.: Can. J. Chem. 50, 2377 (1972)), and the reactions of citraconic anhydride with 1-phenyl-butadiene (Alder, K., Haydn, J., Krüger, B.: Chem. Ber. 86, 1372 (1953) and 6-methoxy-1-vinyl-naphthalene (Bachmann, W. E., Scott, L. B.: J. Am. Chem. Soc. 70, 1462 (1948)). See also Schmidt, C.: J. Org. Chem. 35, 1324 (1970); Schmidt, C., Sabnis, S., D., Schmidt, E., Taylor, D. K.: Can. J. Chem. 49, 372 (1971): A related example with 2-methoxy-6-methyl-benzoquinone and penta-1,3-dien-5-ol has been reported: Gras, J.-L.: Tetrahedron Lett. 1977, 4117

    Google Scholar 

  63. Examples of this type include the cycloadditions of diazomethane and diazoethane to 2-methylnaphthoquinone (Dean, F. M., Houghton, L. E., Morton, R. B.: J. Chem. Soc. (C), 1980 (1967)), various diazoalkanes to citraconic and mesaconic esters (van Auken, T. V., Rinehart, K. L., Jr.: J. Am. Chem. Soc. 84, 3737 (1962)); (Guisgen, R., Eberhard, P., Tetrahedron Lett. 1971, 4343), and triphenylsilyldiazoethane to citraconic anhydride (Brook, A. G., Jones, P. F.: Can. J. Chem. 49, 1841 (1971)). See also El-Ghandour, N., Henri-Rousseau, O., Soulier, J.: Bull. Soc. Chim. France 1972, 2817; Kondo, K., Ojima, I.: Chem. Lett. 1972, 771

    Google Scholar 

  64. Brauman, J. I., Blair, L. K.: J. Am. Chem. Soc. 92, 5986 (1970)

    CAS  Google Scholar 

  65. DeFrees, D. J., Bartmess, J. E., Kim, J. K., McIver, R. T. Jr., Hehre, W. J.: J. Am. Chem. Soc. 99, 6451 (1977) and references therein

    CAS  Google Scholar 

  66. Hudson, R. F., Eisenstein, O., Anh, N. T.: Tetrahedron 31, 751 (1975)

    CAS  Google Scholar 

  67. Tegmo-Larsson, I.-M., Rozeboom, H., Houk, K. N.: work in progress; now indicates that the methoxy group orients cycloadditions in the same fashion as the methyl

    Google Scholar 

  68. Liotta, C. L.: Tetrahedron Lett. 1975, 519, 523

    Google Scholar 

  69. Inagaki, S., Fukui, K.: Chem. Letters 1974, 509

    Google Scholar 

  70. Liotta, C. L., Burgess, E. M.: unpublished results

    Google Scholar 

  71. Caramella, P., Houk, K. N.: unpublished results

    Google Scholar 

  72. Houk, K. N., in: Jones, M., Moss, R. A.: Reactive intermediates. A serial publication, Vol. 1, New York: Wiley 1978

    Google Scholar 

  73. Br2: Grosjean, D., Mouvier, G., Dubois, J.-E.: J. Org. Chem. 41, 3872 (1976), Modro, A., Schmid, G. H., Yates, K.: J. Org. Chem. 42, 3673 (1977)

    CAS  Google Scholar 

  74. carbenes: Moss, R. A., Mallon, C. B., Ho, C.-T.: J. Am. Chem. Soc. 99, 4105 (1977)

    CAS  Google Scholar 

  75. boranes: Brown, H. C., Liotta, R., Snouten, C. G.: J. Am. Chem. Soc. 98, 5297 (1976)

    CAS  Google Scholar 

  76. Battaglia, A., Shaw, S. M., Hsue, Cheng-Sho, Houk, K. N.: submitted for publication

    Google Scholar 

  77. Masclet, P., Grosjean, D., Mouvier, G., Dubois, J.-E.: J. Electron Spectrosc. Rel. Phenom. 2, 225 (1973). In order to compare vertical IP's, 0.16 eV has been added to the adiabatic IP's of substituted ethylenes given by Masclet et al

    CAS  Google Scholar 

  78. Bast, K., Christl, M., Huisgen, R., Mack, W.: Chem. Ber. 106, 3313 (1973)

    Google Scholar 

  79. This is estimated from the fact that the p-nitro compound reacts 5–7 times faster at 20° than the p-methoxy compound at 25°

    Google Scholar 

  80. Domelsmith, L. N., Caramella, P., Houk, K. N.: unpublished results

    Google Scholar 

  81. Sauer, J.: Angew. Chem. Int. Ed. Engl. 5, 211 (1966); 6, 16 (1967); Sauer, J., Mielert, A., Lang, D., Peter, D.: Chem. Ber. 98, 1435 (1965); Sauer, J.: unpublished results

    CAS  Google Scholar 

  82. Gosti-Babaians, H., Houk, K. N.: unpublished results

    Google Scholar 

  83. Houk, K. N., Munchausen, L. L.: J. Am. Chem. Soc. 98, 937 (1976)

    Article  CAS  Google Scholar 

  84. Houk, K. N., George, J. K., Duke, R. E., Jr.: Tetrahedron 30, 523 (1974)

    Article  CAS  Google Scholar 

  85. Paddon-Row, M. N.: Australian J. Chem. 27, 299 (1974)

    CAS  Google Scholar 

  86. Houk, K. N., Luskus, L. J.: J. Org. Chem. 38, 3836 (1973)

    Article  CAS  Google Scholar 

  87. Houk, K. N., Luskus, L. J., Bhacca, N. S.: J. Am. Chem. Soc. 92, 6392 (1970); Bhacca, N. S., Luskus, L. J., Houk, K. N.: Chem. Comm. 1971, 109; Luskus, L. J.: Dissertation, Louisiana State University, Baton Rouge, Louisiana, 1971; Houk, K. N., Luskus, L. J., Bhacca, N. S.: Tetrahedron Lett. 1972, 2297; Tegmo-Larsson, I.-M., Houk, K. N.: Tetrahedron Lett. 1978, 941

    CAS  Google Scholar 

  88. Paddon-Row, M. N., Warrener, R. N.: Tetrahedron Lett. 1974, 3797

    Google Scholar 

  89. Houk, K. N., Luskus, L. J.: Tetrahedron Lett. 1970, 4029

    Google Scholar 

  90. Padwa, A., Nobs, F.: Tetrahedron Lett 1978, 93

    Google Scholar 

  91. Dunn, L. C., Chang, Y.-M., Houk, K. N.: J. Am. Chem. Soc. 98, 7095 (1976)

    Article  CAS  Google Scholar 

  92. Reiter, S. E., Dunn, L. C., Houk, K. N.: J. Am. Chem. Soc. 99, 4199 (1977); see also Copland, D., Leaver, D., Menzies, W. B.: Tetrahedron Lett. 1977, 639

    Article  CAS  Google Scholar 

  93. Sato, M., Ebine, S., Tsunetsugu, J.: Tetrahedron Lett. 1974, 2769

    Google Scholar 

  94. Caramella, P., Frattini, P., Grünanger, P.: Tetrahedron Lett. 1971, 3817

    Google Scholar 

  95. Mukherjee, D., Dunn, L. C., Houk, K. N.: J. Am. Chem. Soc., in press

    Google Scholar 

  96. Dunn, L. C., Houk, K. N.: Tetrahedron Lett. 1978, 3411

    Google Scholar 

  97. Huisgen, R.: private communication

    Google Scholar 

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  1. Department of Chemistry, Louisiana State University, 70803, Baton Rouge, Louisiana, USA

    Kendall N. Houk

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Houk, K.N. (1979). Theoretical and experimental insights into cycloaddition reactions. In: Organic Chemistry. Topics in Current Chemistry, vol 79. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0048475

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  • DOI: https://doi.org/10.1007/BFb0048475

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